HK1119441B - Toner - Google Patents

Description

Toner for developing electrostatic image

This application claims benefit of provisional application No. 60/758,757 filed on day 13, 1/2006 and provisional application No. 60/663,422 filed on day 18, 3/2005.

The contents of said provisional application are included herein by reference.

Background

Briefly stated, there is a need for improved toners for office copiers or laser printers that can be positively or negatively charged. The improvements sought are in terms of improved flow and wetting, lower energy for fusing, toner removal from office waste paper, and toner resins derived from renewable resources. As a large share of the copier and printer markets use such toning systems, there is a greater interest in the ability of resins to inherently provide a negative charge to tone a positively charged latent electrostatic image. Conventional toners are based on synthetic resins, such as styrene acrylates, polyesters, polyamides, and the like. Resins derived from renewable resource feedstocks such as corn, soybeans, and other plants are gaining increasing attention due to the problems associated with the environmentally sustainable long-term supply of petroleum-derived resins. Examples of bio-based resins are derived from dimer acid and D-isosorbide, which have good hue and print characteristics like current petroleum resin-derived toners.

There is also a need for a toner having the ability to disperse pigments in a combined resin. The use of biogenic polyester resins derived from dimer acid and D-isosorbide in powder coating formulations gives a final coating with improved pigment dispersion. There is also a need for resins that flow at lower fixing temperatures to minimize energy consumption for operating a copier machine.

There is great interest in replacing some petrochemical feedstocks with feedstocks of biological origin for a wide range of applications. Evidence of this interest is reflected in the number of review articles that have been published over the years. An example of an attempt to utilize biogenic sources in the synthesis of polyester resins is given in U.S. Pat. No. 6,063,464, where isosorbide derived from corn biomass is used in the synthesis of polyester materials.

Related art includes US patents US 5,959,066, US 6,025,061, US 6,063,464 and US 6,107,447.

Brief description of the invention

Generally, the present invention provides a toner having a negative or positive charge. The toner is typically used in electrostatic type copiers and printers.

A first embodiment of the present invention provides a toner comprising a colorant (coloring agent) and a thermoplastic polymer. Typically, the toner includes particles having an average particle size range of less than about 30 microns, more preferably an average particle size range of less than about 25 microns, and most preferably an average particle size range of less than about 20 microns. Typically, excipients selected from the group consisting of charge control agents, flow control agents, lubricants, anti-caking agents, and mixtures thereof are used. In some exemplary embodiments, the toner has a negative triboelectric charge (tribo-electric charge) of between about 10 and about 40 microcoulombs/gram, and more preferably between about 10 and about 20 microcoulombs/gram. Some exemplary embodiments provide a toner having a polymer glass transition temperature between about 50 ℃ and about 70 ℃.

In one embodiment of the invention, the toner is used with printing and copying paper.

In still a further embodiment of the present invention, there is provided a method for producing a negatively or positively charged toner by the step of compounding a colorant and a thermoplastic polymer. Typical toner compounding involves powder mixing on a hot roll mill or extrusion of the polymer resin for the toner with the dispersed colorant. Typically, the compounded toner is micronized and, if necessary, classified for an appropriate particle size distribution according to the application.

Another embodiment of the present invention provides a toner comprising a toner selected from the group consisting of (1) a carboxyl or hydroxyl functional polyester; (2) a polyester ether; (3) an amorphous thermoplastic polymer of the group consisting of polyurethanes; and wherein the polymer is derived from at least one organismA source monomer; and the polymer has a T between about 50 ℃ and about 80 ℃_g(ii) a b. A colorant; and wherein the toner comprises a powder having an average particle size of less than about 30 microns. In one embodiment, the carboxy functional polyester is derived from a didehydrohexitol moiety (e.g., an isosorbide moiety), a first diacid moiety, and/or a second diacid moiety, optionally further comprising a monoacid. In a further embodiment, the isosorbide moiety is D-isosorbide, the first diacid is 1, 4-cyclohexanedicarboxylic acid, and the second diacid is a long chain diacid having 8 or more carbon atoms in the chain.

Another embodiment of the present invention provides a toner comprising a toner selected from the group consisting of (1) a carboxyl or hydroxyl functional polyester; (2) a polyester ether; (3) an amorphous thermoplastic polymer of the group consisting of polyurethanes; and wherein the polymer is derived from at least one monomer of biological origin; and the polymer has a T between about 50 ℃ to about 80 ℃_g(ii) a b. A colorant; and wherein the toner comprises a powder having an average particle size of less than about 30 microns. In one embodiment, the carboxy functional polyester is derived from dianhydrohexitol (e.g., isosorbide) moieties, first diacid moieties, and/or second diacid moieties, optionally further comprising a monoacid. In a further embodiment, the isosorbide moiety is D-isosorbide, the first diacid is 1, 4-cyclohexanedicarboxylic acid, and the second diacid is a long chain diacid having 8 or more carbon atoms in the chain.

In still further embodiments, the toner includes (1) a thermoplastic polyester resin that is a. dianhydrohexitol; B. dimer diol and/or dimer diacid; C. a diacid, diester or diacid chloride; and d. optionally a catalyst; and (2) a pigment.

In another embodiment of the present invention, there is provided a developer comprising:

(1) a thermoplastic polyester resin comprising the reaction product of:

A. a dianhydrohexitol; B. dimer diol and/or dimer diacid;

C. a diacid, diester or diacid chloride; optionally a catalyst;

(2) a pigment; and

(3) and (3) a carrier.

In some embodiments, the developer comprises a magnetic material.

In a still further embodiment of the present invention, images are provided that are prepared with negatively or positively charged toner compositions comprising a colorant and a thermoplastic polymer.

Brief description of the drawings

FIG. 1 is a schematic flow diagram showing a synthetic route to a polyester material for blending hard, crystalline isosorbide with amorphous dimer diol, aromatic diester and other ingredients.

FIG. 2 is a schematic flow diagram showing a synthetic route to polyester acids blending hard, crystalline isosorbide and amorphous dimer diol with other ingredients. It is particularly useful for toners.

Fig. 3 is a schematic flow diagram showing a synthetic route to polyurethane that blends hard, crystalline isosorbide with dimer diol, amorphous dimer diacid, polyisocyanate (e.g., diisocyanate), and other ingredients.

FIG. 4 illustrates typical isomers of isosorbide useful in the present invention (1a, 1b and 1 c).

Fig. 5 is a schematic diagram showing various components of an apparatus for manufacturing resin examples 1 to 3F.

Fig. 6 is a graph illustrating the rheology curves of biogenic resin examples 1 and 3C, wherein the horizontal axis is the draw down rate (1/sec) and the vertical axis shows the viscosity in Poise (Poise). These resins of biological origin are typical of those used in toners.

Detailed description and best mode of the invention

In general, the present invention combines the desired application of a biologically-derived feedstock with the need for a biologically-derived toner. Corn and soy raw materials can be utilized to make resins with property tradeoffs appropriate for toner performance. These resins can then be formulated into various toner formulations.

Typically, in one embodiment, a toner according to the present invention is prepared as follows: pulverizing the primary resin, dry blending the pulverized colorant and the selected pulverized additive; additional micronization may be employed. In a preferred embodiment, the polymer resin is mixed with the colorant, extruded and micronized. This blend may be micronized or pulverized to the desired particle size, and the resulting toner powder is ultimately classified as the final particle size. For application to a substrate, the carrier is typically mixed with a toner, and after application, the carrier is typically separated from the substrate.

A product of biological origin as used in some embodiments of the invention refers to a product derived at least in part from renewable resources based on agriculture or forestry, with conventional chemical modification and/or conversion of biological processes such as fermentation, for example. Carbon sources are derived from renewable plant crop/tree resources, unlike carbon sources from conventional fossil sources that are limited and rapidly depleting.

There are many polymer properties that are important to toner performance. Among the key properties of interest are:

negative or positive triboelectric charges targeted at 10 to 40 microcoulombs/gram. Because image quality is affected by charge levels, negative or positive triboelectric charges of greater than about 10 microcoulombs/gram are typically required to produce an acceptable copy.

Glass transition temperature of polymer targeted at 50 ℃ to 70 ℃ ((T_g). Acceptable fixing and blocking resistance (i.e., toner powder clumping upon storage) is strongly affected by T_gIs strong.

A base toner composition of 10% carbon and 90% polymer is used herein. However, any desired ratio of colorant to polymer can be selected so long as the toner provides the desired properties of adhesion, fusing, etc. to retain the colorant on the substrate to which it is applied. Other additives, mentioned below, may be included in a typical toner to achieve desired toner properties. Given the teachings of the present invention, one skilled in the art will be able to select additives and materials to achieve the desired charge properties.

Flow control agent-is used to provide good powder flow. Examples include fumed silica (fumed silica) and fine abrasive particles.

Surface additives-typically lubricants to prevent toner from fouling the fuser roller, cleaning aids, triboelectric charging; toner flow and handling; for example, Aerosil (R972), titana (P25) to provide triboelectric charge stability, zinc stearate which acts as a charge rate modifier and acts as a blade cleaner lubricant; kynar (fluoropolymer) as a lubricious additive.

Colorant-black, such as carbon black, magnetite, or a combination of the two; adding a bright color and a full color domain; typical color pigments, cyan-substituted metal phthalocyanines, magenta-quinacridones, azonaphthols (azonapthols), aminofluorenes (xanthenes), disazo derivatives of yellow, diaminobiphenyls, monoazo compounds.

Diffusant (dispersal agent) -and additives that prevent or reduce pigment aggregation and provide more complete development of the colorant in the toner. In the present invention, certain resins can be used as internal diffusants, such as the material in example 3F.

Bulking agent-fixation and release promoting agents, for example, waxes.

Magnetic additives-are commonly used for toner containment, developability, color, cleaning.

Conductive and non-conductive additives, which are typically added to control the conductivity of the toner. For example, silica may be added to control the conductivity of the carbon black.

Charge control agents-added to provide the correct sign and magnitude of triboelectric charge; a controlled rate of charge; fusing parameters and fuser life; for example Aerosil R972.

Typical thermoplastic polymers (and monomers thereof) that may be used in the present invention either alone or as a blend added to the main component include: polyamides, polyesters, polyester ethers, polyurethanes, blends with acrylates or polyamides, and mixtures thereof. The styrene content in polystyrene acrylates may be useful for controlling the negative charge. Polystyrene acrylates having higher styrene content are expected to increase the amount of negative charge when incorporated into the polymers herein.

A mixture as used herein may be a collection of components or materials substantially uniformly dispersed therein; typically, because one component is a thermoplastic polymer, the components or materials are melt blended together.

Polymerization degree-it has been found by tests herein that the best materials have a polymerization degree that provides a toner in a solid state at room temperature and that is easy and quick to handle at typical toner temperatures. The material should flow easily to paper or other substrate and be heated to its T_gAdhesion is good above temperature. Typical degrees of polymerization include 5-80 units. The material should not be brittle in order to avoid breakage and the creation of unwanted dust.

Additionally, blends of polymers of different molecular weights can be used to provide desirable melt rheology for acceptable fusing behavior. In the various embodiments herein, the additives used are minimized; generally, fumed silica (fumed silica) may be added to aid in powder flow to achieve good magnetic brush formation. The commonly used base toner component is 90% resin and 10% carbon black. Regal 330, RAVEN and carbon black from Cabot corp.

Resins particularly useful according to the present invention have a good balance of two clearly contradictory properties:

(1) low viscosity upon melting, which is characteristic of amorphous resins, for good flow-out upon application, but must also have,

(2) relatively high glass transition temperature (T) for good storage stability_g) This is characteristic of crystalline resins. If T is_gToo low, the powder particles can be "soft" and agglomerate into unusable lumps upon storage, especially at elevated storage temperatures. Typically, these properties are balanced by blending crystalline and amorphous resins into an effective semi-crystalline resin blend. Typical resins obtained according to the present invention provide these desirable properties.

Note that: unless otherwise specified,% when referring to the amount of an ingredient means weight percent (wt.%).

There are three main general synthetic routes for the invention disclosed herein to resin and useful:

1. hydroxyl-functional polyesters based on dimer diol, diol derived from isosorbide and/or dimer acid. Typically, the carboxyl or hydroxyl functionality of the polyester is determined by the ratio of molar excess of diacid or diol groups. Polyesters typically have a net biogenic content of at least about 5% by weight, but most typically have from about 20 to about 50% by weight.

2. Carboxyl-functional polyesters based on dimer diol, diol derived from isosorbide and/or dimer acid. Typically, the carboxyl or hydroxyl functionality of the polyester is determined by the ratio of the molar excess of diacid or diol groups. The polyester typically has a net biogenic content of at least about 5% by weight, but most typically has from about 50 to about 70% by weight.

The polyester polyol resins disclosed herein are useful in toners and pigment dispersing agents.

The present invention also relates to the use of one or more of these biogenic materials in a variety of applications, including but not limited to toners. The resin for one embodiment is designed to have suitable melt rheology with a glass transition temperature (T) of less than about 80 ℃_g) Other embodiments have a glass transition temperature (T) of less than about 70 ℃_g) There are other embodiments that are less than about 60 ℃. Resins according to a broad embodiment of the invention have a minimum glass transition temperature of at least about 20 ℃ and a maximum of about 80 ℃ and have suitable melt rheology. Typically, resins useful for flow control are at the lower end of the glass transition temperature range (e.g., where T is_gExample 3B) at about 28.4 ℃, but the temperature may vary in the range of about 20 ℃ to about 80 ℃, and in certain embodiments, may typically be about 25 ℃ to about 60 ℃. Low T_gThe material can be mixed with high T_gThe materials are mixed to provide a variety of properties.

The resin according to the invention may be composed of co-reactive components tending to contribute to a stiffening (rigidifying) effect, such as isosorbide (typically from corn feedstocks) and components contributing to a toughening (flexibilizing) effect, such as dimer acid or dimer diol (typically from vegetable oil feedstocks). By properly co-reacting these components into a resin, both the flow-out property and storage stability of the resin can be controlled. Generally, the hardening component comprises chemical functional groups, such as alcohols, esters, carboxylic acids or acid chlorides, linked to cyclic structures that limit their mobility, while the toughening component comprises chemical functional groups linked to aliphatic carbon chains. Isosorbide, a diol composed of fused multiple cyclic ether rings, is a member of a larger family of biogenic sugar derivatives (commonly referred to as dianhydrohexitols). Dimer acids and dimer diols are dicarboxylic acids and diols, respectively, derived from fatty acids of biological origin, which are, in fact, predominantly aliphatic. Similarly, these stiffening and toughening effects are also applicable to the polyurethane as depicted in FIG. 3.

The invention also relates to the formulation of toners from one or more of the inventive resins. The unique properties of one toner embodiment are negative charge, good flow, good fixing ability, and good pigment dispersion.

A key characteristic of the resins used in toner formulations is the glass transition temperature (T)_g) Typically at least about 50 c, and preferably at least about 60 c for storage stability of the final toner powder. Table 1 shows several soy-based resins, their functional groups and their T_gA list of (a). This table illustrates the production of acceptable T from materials comprising low viscosity soy-based monomers_gThe difficulty of the resin of (2).

Only resin 1 satisfies T_gThe standard of (2). In order to achieve a higher T_gAnd maintaining a high loading of biogenic material in the resin, using another material having a high intrinsic T_gThe contributing biogenic material is isosorbide.

E.g. with a higher T_gIs identified as co-reactive with soy-based materials to give materials of high biogenic content and sufficiently high T_gFor use in toner formulations. The soy-based material and other ingredients may be selected to achieve an appropriate balance of properties in the resins and ultimately the toner.

Synthesis of the resin (see examples 1 and 2):

the use of biogenic materials in the production of toners can be described as follows:

a polyester polymer is prepared by the steps of: (1) mixing isosorbide (derived from corn feedstock) in a reactor; aliphatic dimer diol and/or dimer diacid (derived from soy source); a diacid, diester or diacid chloride; optionally one or more co-diols (co-diol); and optionally one or more co-diacid, one or more co-diester or one or more co-diacid chloride and a condensation catalyst suitable for polymerizing aromatic diacid and diol; and (2) heating the monomers and catalyst to polymerize the monomers to produce a polyester (see fig. 1).

A carboxyl-functional polyester resin is prepared by the following steps: (1) mixing isosorbide in a reactor; an aliphatic dimer diacid; optionally one or more co-diacid, one or more co-diester or one or more co-diacid chloride; and optionally a co-diol; and a condensation catalyst; and (2) heating the monomers and catalyst to polymerize the monomers to produce a carboxyl functional polyester resin (see fig. 2).

Hydroxyl-, carboxyl-or isocyanate-functional polyurethanes are prepared by the following steps: (1) mixing isosorbide in a reactor; aliphatic dimer diacid and/or dimer diol; a polyisocyanate; optionally one or more co-diols; and optionally one or more co-diacid, one or more co-diester or one or more co-diacid chloride, with or without a catalyst suitable for polymerizing diols and diacids with the polyisocyanate; and (2) heating the monomers and optional catalyst to polymerize the monomers to produce polyurethane (see fig. 3).

Referring now to fig. 1, 2 and 3, various reactants for use in embodiments of the present invention are disclosed. In addition to the dimer diol and dimer acid disclosed, the present invention according to a broad embodiment comprises an aliphatic chain typically having from about 4 to about 20 carbon atoms. More preferably, the aliphatic chain has from about 6 to about 16 carbon atoms.

Still further disclosed dimer diols and dimer acids include a six-membered ring having two side chains that are aliphatic side chains of about 4 to 20 carbon atoms and two additional side chains of about 8 to 12 carbon atoms with alcohol or carboxyl functionality.

Additionally, the diesters, diacids, co-diacids, and co-diesters can have the general formula R₂-CO-R₁-CO-R₂Wherein R is₂＝-OH、-OR₃or-Cl, wherein R₃An aliphatic chain having 1 to 4 carbon atoms. R₁May be an aromatic group or an aliphatic group having 2 to 12 carbon atoms.

While not wishing to be bound by theory, it is presently believed that the pendant aliphatic chains in dimer acid and dimer diol provide the resin with low viscosity properties. The pendant aliphatic chains tend to soften at low temperatures, resulting in reduced viscosity and better flow. The longer the chain, the more softening can be seen, and the faster it softens when heated.

As shown in example 9, it is also believed to provide improved pigment dispersion in some embodiments. One result of better flow is superior pigment wetting, thereby improving pigment dispersion.

Additionally and more broadly, dianhydrohexitols may be used in the present invention. Thus, other dianhydrohexitols may be used in place of D-isosorbide or its isomers in the preparation of the hardened structures by incorporating bicyclic systems comprising other cyclic diols. Diols incorporating cyclohexyl, isophorone and other ring structures can increase the hardening effect similar to isosorbide.

Dimer diacids are typical of C₁₈Dimerization of unsaturated fatty acids results in a viscous liquid. C₁₈Unsaturated fatty acids have three biological sources; plants, tall oil and animals. Said C is₁₈The units may be connected together in several ways. 4 main structural types are due to the main component C₃₆Diacids are well known, i.e. acyclic, monocyclic, bicyclic andis aromatic. There are also many structural isomers for each of these structural types. The type of structure and distribution of isomers depends on the mono/poly-unsaturation ratio of the starting fatty acid feedstock and the process conditions employed for dimerization. The smallest dimer diacid typically used in some embodiments is C₁₈A dibasic acid.

Four types of dimer diacids are currently commercially available: (1) standard (undistilled), containing about 80% C₃₆A dibasic acid; (2) distilled, of which C is₃₆The content of the dibasic acid is improved to 92-98 percent; (3) distilled and partially hydrogenated to improve color; and (4) distilled and fully hydrogenated to achieve maximum stability.

The dimer acid used to prepare the polyester resin of biological origin is EmpolExamples 3 and 3C and(example 2), both are plant-based dimer acids. EmpolManufactured by Cognis corporation, PripolIs manufactured by Uniqema. Cognis has stopped their production of plant-based dimer acid, supporting tall oil-based dimer acid. Table 1A compares PripolAnd EmpolPhysical properties and composition of (a). PripolLighter in color and with higher diacid content. The carboxyl functional resins obtained with these two different dimer acids have similar physical properties.

TABLE 1A compositions and Properties of dimer acids

Dimer diols are generally produced by high pressure hydrogenation of dimer diacid methyl esters. The dimer diol used to prepare the biogenic polyester resins (examples 1, 1A and 3B) is SPEZIOL C36/2A dimer diol. This is a plant-based dimer diol produced by Cognis.

The disclosed resins have a lower viscosity once melted relative to commercial petrochemical-based resins (see examples). In toner formulations, it is desirable to add flowable materials (flow control additives) to achieve good fusing and other acceptable copy properties. The biogenic resins require little or no such additives to achieve good film flatness and appearance. The biogenic resins themselves may also function as flow additives in formulations comprising conventional petrochemical-based resins, which were successfully added in formulations comprising conventional petrochemical-based resins.

The polyester polymers of the present invention are prepared by reacting isosorbide, dimer diol and/or dimer acid, diacid, diester or diacid chloride; optionally one or more co-diols; optionally one or more co-diacid, one or more co-diester, or one or more co-diacid chloride (from the process of figure 1).

A typical procedure for preparing a hydroxy-functional polyester is described in example 1. Aliphatic polyesters are soft, flexible, rubbery materials. Most aromatic polyesters are crystalline. Blending soft dimer diol with highly functionalized isosorbide and with crystalline aromatic diacid can result in a good balance of properties. However, this equilibrium can also be assisted by including other materials in the reaction, such as ethylene glycol (i.e., "glycol" of FIGS. 1 and 2).

By preparing a glass transition temperature (T) having a range of from 61 ℃ to 165 ℃_g) The effect of the polyesters of (a) on various monomers was investigated (tables 2A and 2B). Table 2A shows typical properties of resins synthesized as described herein and having a glass transition temperature (T) of from 61 ℃ to 165 ℃_g) The various monomers of (a). Table 2B shows typical properties of carboxyl functional resins synthesized as described in examples 2-3.

The data show the possible T's using these monomers_gTo a large extent. The test polyesters prepared without isosorbide are not amorphous like those containing isosorbide, but crystalline in properties.

D-isosorbide (1, 4: 3, 6-dianhydro-D-glucitol) (1a) or its isomers and/or mixtures of all isomers, including D-isosorbide, can be used in place of D-isosorbide. 1,4: 3, 6-dianhydro-D-mannitol (1b) and 1, 4: 3, 6-dianhydro-D-iditol (1c) is two isomers of isosorbide. D-isosorbide is used in the present invention, but isomers of D-isosorbide are expected to work as well. Isomers of isosorbide useful in the present invention are illustrated in figure 4.

Examples of suitable acid functional polyester forming polyols include: 1, 2-ethanediol (ethylene glycol), 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, neopentyl glycol, trimethylolpropane, hydrogenated bisphenol A (2, 2- (dicyclohexylol) propane), 2, 4-trimethyl-1, 3-pentanediol, 2-methyl-1, 3-propanediol, 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2-ethyl-2-hydroxymethyl-1, 3-propanediol, and the like, and combinations comprising at least one of the foregoing polyols. Since the goal of current work is to maximize biomass content, the preferred polyols are isosorbide (from corn feedstock) and dimer acid diol (from soy feedstock), ethylene glycol, although others may be used to improve properties as desired.

Suitable polycarboxylic acids, acid esters and acid chlorides include those derived from: succinic acid, adipic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, terephthalic acid, isophthalic acid, trimesic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1, 4-cyclohexanedicarboxylic acid, trimellitic acid, naphthalenedicarboxylic acid, dimer acid, and the like, as well as combinations comprising at least one of the foregoing polycarboxylic acids. The preferred diester is the dimethyl ester of terephthalic acid. Dodecanedioic Acid (DDA) is used as a modifier in several formulations. Diacids such as 1, 4-cyclohexanedicarboxylic acid, Empol、PripolEtc. may also be used. Preferred diacids have a long chain to provide flexibility, and thus dimer acids having eight (8) or more carbon atoms in the chain are preferred.

To obtain a carboxyl functional polyester having the desired molecular weight, the monomer mixture used to form the polyester typically has a suitable excess of carboxyl functionality to hydroxyl functionality, with the ratio of hydroxyl equivalents to acid equivalents typically being 0.85 to 0.95. Typically, the polyester is amorphous.

Referring now to FIG. 5, there is shown the various components of an apparatus 100 for making resin according to the present invention. A heating mantle 102 at least partially surrounds the reactor 101 for controlling the temperature of the reactor 101 containing the reaction mixture 104. The reactor 101 is comprised of a reaction vessel 106 and a top 108. The top 108 has a plurality of necks 110, 112, 114, 116 for connection to various appliances. Agitation is provided by a paddle 120 (e.g., typically a 45 ° angled blade) at the end of an agitator shaft 122 (e.g., stainless steel). The agitator shaft 122 passes through the neck 116. A thermocouple controller 130, connected to a thermocouple 132 by a connector 131, enters the reaction mixture 104 through the neck 110 at a gas inlet connector 111 of the sealed fitting. A vigreux column 140 is mounted in sealing relation to the neck 114. A thermometer 141 or other temperature measuring device is mounted on the top (distillation head) 142 of the wiggler column 140. The condenser 150 is mounted to the neck 144 of the wiggler column 140 through a condenser inlet 152 using a connector 146. The wiggler column 140 may be a separate unit surrounded by a sheath or the sheath and column are integral. The condenser outlet 154 is connected to a neck inlet 162 of a neck 160, the neck 160 having a gas outlet 164, a neck outlet 166. Receiving flask 170 has an inlet 172 connected to neck outlet 166. The cooling fluid 155 enters the condenser 150 at an inlet 156 and exits at an outlet 158.

In operation, argon gas 111-1 enters at gas inlet connector 111 to cover reaction mixture 104 and exits at gas outlet 164. These components may be added before the device is closed or through a sealed connector 118 at the neck 112. Note that in fig. 5, the neck 112 is located directly behind the neck 116. The neck 112 is located on the central axis 190 of the reactor 101. Distillate 178 is collected in receiving flask 170.

The following examples are intended as illustrations of aspects of the invention and are not intended to limit the scope of the invention in any way.

Production of the resin (examples 1 to 3F)

Example 1

This example illustrates the production of a hydroxy-functional bio-derived polyester resin.

Equipment (see figure 5)

A 1-liter 4-necked cylindrical walled round bottom glass flask, jacketed wiggler column, distillation head, inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with dimethyl terephthalate (DMT) (228.30g, 1.1757 moles), Speziol C36/2Dimer diol (run #415252) (77.61g, 0.1411 moles), D-isosorbide (123.90g, 0.84785 moles) and Ethylene Glycol (EG) (102.81, 1.6563 moles), followed by manganese (II) acetate tetrahydrate (0.0917 g), cobalt (II) acetate tetrahydrate (0.0618g) and antimony (III) oxide (0.103 g). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 ℃ (1.6 ℃/min) over a period of 30 minutes. This temperature is maintained for 30 minutes or until the temperature at the top of the Viger column falls to 30 ℃ or less. Methanol was collected continuously as the reaction was heated above about 150 ℃. When the temperature at the top of the column dropped, it indicated that methanol had been removed. About 95ml of methanol was distilled off. Next, a solution of polyphosphoric acid (0.0634g) in EG (1g) was added to the reaction mixture. The flow rate of argon over the reaction mixture was checked and, if necessary, reduced to a slow flow rate to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (0.25 deg.C/min) over a 2 hour period. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. During this time, the ethylene glycol was distilled off (91g), anda low molecular weight polymer is formed. The reaction mixture temperature was maintained at 280 ℃ for 3 hours and 10 minutes. The reaction was terminated by blanketing the reaction mixture with argon to maintain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

intrinsic viscosity of the solution: 0.29 (the solvent is o-chlorophenol, only 92% soluble)

T_g＝61℃

Hydroxyl number 24.3

Acid value of 8.0

Molecular Weight (MW) ═ 3470 (calculated as acid number and hydroxyl number)

The polymer is characterized in that:

color: brown colour

Viscosity: non-stick

Transparency: slightly translucent

Flexibility: crisp

Solid state

Example 1A

This example illustrates the production of a polyester resin of biological origin.

Apparatus (see fig. 5):

a 1-liter 4-necked cylindrical walled round bottom glass flask, jacketed wiggler column, distillation head, inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with dimethyl terephthalate (DMT) (197.74g, 1.0183 moles), D-isosorbide (119.0)5g, 0.81463 mol) and Speziol C36/2Dimer diol (run #415252) (112.06g, 0.20371 moles) followed by 1, 2, 3, 4-tetrahydronaphthalene (2ml) and antimony (III) oxide (0.089 g). The reactor was blanketed with argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 12 minutes. The reaction mixture was slowly heated to 250 ℃ (2.5 ℃/min) over a 20 minute period. This temperature was maintained for 8 minutes. Methanol was collected continuously as the reaction was heated above about 150 ℃. When the temperature at the top of the vigreux column drops, it indicates that methanol has been removed. About 83ml of methanol are distilled off. The flow rate of argon over the reaction mixture was checked and, if necessary, reduced to a slow flow rate to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (2.3 deg.C/min) over a period of 13 minutes. The reaction mixture was then allowed to cool to 260 ℃. Additional D-isosorbide (14.87g, 0.1018 moles) was added to the reaction mixture. The reaction mixture was heated to 280 ℃. This temperature was maintained for 30 minutes. The distillate receiver was replaced with a vacuum receiver and vacuum was gradually applied (< 9 torr). During this time, a low molecular weight polymer is formed. The temperature of the reaction mixture was maintained at 280 ℃ for 2 hours and 40 minutes. The reaction was terminated by blanketing the reactants with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

intrinsic viscosity of the solution: 0.10 (the solvent is o-chlorophenol)

T_g＝165℃

Hydroxyl number 45.0

Acid value of 2.3

Molecular Weight (MW) ═ 2372 (calculated as acid number and hydroxyl number)

The polymer is characterized in that:

color: light brown

Viscosity: glue stick

Transparency: semi-transparent

Flexibility: is a bit crisp

Solid state

Example 2

This example illustrates the production of a carboxyl functional bio-derived polyester resin.

Apparatus (see fig. 5):

a 5 liter round bottom glass reaction vessel with a 4 neck top, jacketed wiggler column, distillation head, gas inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with D-isosorbide (1337.0g, 9.1490 moles) (calculated as received), PripolDimer acid (batch No. 091687) (699.1g, 1.215 moles), 1, 4-cyclohexanedicarboxylic acid (1, 4-CHDA) (1563.8g, 9.0826 moles), followed by antimony (III) oxide (1.231 g). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 deg.C (1.1 deg.C/min) over a period of 47 minutes. This temperature was maintained for 3.1 hours or until the temperature at the top of the Vigrella column was reduced to 30 ℃ or less. Water was collected continuously as the reaction was heated above about 180 ℃. When the temperature at the top of the wiggler column drops, it indicates that most of the water has been removed. About 329ml of water was distilled off. Checking the reaction mixture for argonFlow rate and reduced to a lower flow rate if necessary to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (0.25 deg.C/min) over a 2 hour period. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. At this time, residual water was distilled off, and a low molecular weight polymer was formed. The reaction mixture temperature was maintained at 280 ℃ for 3 hours 10 minutes. The reaction was terminated by covering the reaction mixture with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

T_g＝64.2℃

acid value of 34.8

Molecular Weight (MW)

GPC (polystyrene Standard) M_n＝1689

GPC (polystyrene Standard) M_w＝11681

Polydispersity (M)_w/M_n)＝6.91

The polymer is characterized in that:

color: light amber color

Viscosity: non-stick

Transparency: semi-transparent

Flexibility: crisp

Solid state

Example 3

This example illustrates the production of a carboxyl functional bio-derived polyester resin.

Equipment (see figure 5)

A 1 liter 4-necked cylindrical walled round bottom glass flask, jacketed wiggler column, distillation head, gas inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with 1, 4-cyclohexanedicarboxylic acid (1, 4-CHDA) (204.66g, 1.1886 moles), EmpolDimer acid (batch No. U42G151910) (72.54G, 0.1251 mol) and D-isosorbide (172.80G, 1.1824 mol), followed by antimony (III) oxide (0.1594G). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 ℃ (1.6 ℃/min) over a period of 30 minutes. This temperature was maintained for 30 minutes or until the temperature at the top of the Viger column was reduced to 30 ℃ or less. Water was collected continuously as the reaction was heated above about 180 ℃. When the temperature at the top of the column drops, it indicates that most of the water has been removed. Approximately 47ml of water was distilled off. The flow rate of argon over the reaction mixture was checked and, if necessary, reduced to a slow flow rate to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (0.25 deg.C/min) over a 2 hour period. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. During this time, residual water is distilled off and low molecular weight polymers are formed. The temperature of the reaction mixture was maintained at 280 ℃ for 3 hours and 10 minutes. The reaction was terminated by blanketing the reaction mixture with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

intrinsic viscosity of the solution: 0.25dl/g (the solvent is o-chlorophenol)

T_g＝66.9℃

Hydroxyl number 13.0

Acid value of 36.3

Molecular Weight (MW)

GPC (polystyrene Standard) M_n＝2995

GPC (polystyrene Standard) M_w＝9560

Polydispersity (M)_w/M_n)＝3.19

The polymer is characterized in that:

color: light brown

Viscosity: non-stick

Transparency: mostly translucent

Flexibility: is crisp and hard

Solid state

Example 3B

This example illustrates the production of a hydroxy-functional bio-derived polyester resin.

Equipment (see figure 5)

A 1-liter 4-necked cylindrical walled round bottom glass flask, jacketed wiggler column, distillation head, inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with dimethyl terephthalate (DMT) (228.30g, 1.1757 moles), Speziol C36/2Dimer diol (batch No. 415252) (129.40g, 0.23523 moles), D-isosorbide (123.90g, 0.84785 moles), and Ethylene Glycol (EG) (89.66 g, 1.444 moles), followed by manganese (IIA) acetate tetrahydrate (0.0917 g), cobalt (II) acetate tetrahydrate (0.0618g)And antimony (III) oxide (0.103 g). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ by stirring under argon (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 ℃ (1.6 ℃/min) over a period of 30 minutes. This temperature was maintained for 30 minutes or until the temperature at the top of the Viger column was reduced to 30 ℃ or less. Methanol was collected continuously as the reaction was heated above about 150 ℃. When the temperature at the top of the Vigrella column decreased, it indicated that most of the methanol had been removed. About 95ml of methanol was distilled off. Next, a solution of polyphosphoric acid (0.0634g) in EG (1g) was added to the reaction mixture. The flow rate of argon over the reaction mixture was checked and, if necessary, reduced to a slow flow rate to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (1 deg.C/min) over a period of 30 minutes. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. During this time, the ethylene glycol was distilled off (84g), forming a low molecular weight polymer. The reaction mixture temperature was maintained at 280 ℃ for 3 hours and 10 minutes. The reaction was terminated by blanketing the reaction mixture with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

intrinsic viscosity of the solution: 0.19 (the solvent is o-chlorophenol)

T_g＝28.4℃

Hydroxyl number 35.4

Acid value of 6.1

Molecular Weight (MW) ═ 2700 (calculated from acid number and hydroxyl number)

The polymer is characterized in that:

color: brown colour

Viscosity: non-stick

Transparency: mostly translucent

Flexibility: crisp

Solid state

Example 3C

This example illustrates the production of a hydroxy-functional bio-derived polyester resin.

Equipment (see figure 5)

A 1 liter 4-necked cylindrical walled round bottom glass flask, jacketed wiggler column, distillation head, gas inlet and outlet adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with dimethyl terephthalate (DMT) (213.96g, 1.1018 moles), EmpolDimer acid (run No. U42G151910) (71.02G, 0.1225 moles), D-isosorbide (128.79G, 0.88128 moles) and Ethylene Glycol (EG) (116.28G, 1.8734 moles), followed by manganese (IIA) acetate tetrahydrate (0.0859G), cobalt (II) acetate tetrahydrate (0.0579G) and antimony (III) oxide (0.0965G). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 ℃ (1.6 ℃/min) over a period of 30 minutes. This temperature was maintained for 30 minutes or until the temperature at the top of the Viger column was reduced to 30 ℃ or less. Methanol was collected continuously as the reaction was heated above about 150 ℃. When the temperature at the top of the column drops, it is an indication that most of the methanol/water mixture has been removed. Approximately 93ml of the methanol/water mixture were distilled off. Next, a solution of polyphosphoric acid (0.0594g) in EG (1g) was added to the reaction mixture. Check the flow rate of argon over the reaction mixture and reduce it if necessaryTo a slow flow rate to avoid distilling off the isosorbide. The reaction mixture was slowly heated to 280 deg.C (0.25 deg.C/min) over a 2 hour period. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. During this time, the ethylene glycol was distilled off (95g) and a low molecular weight polymer was formed. The reaction mixture temperature was maintained at 280 ℃ for 3 hours and 10 minutes. The reaction was terminated by blanketing the reaction mixture with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 250 ℃ or less and poured onto a fluorinated fiberglass plate.

A resin was produced having the following properties:

intrinsic viscosity of the solution: 0.23 (the solvent is o-chlorophenol)

T_g＝58.8℃

Hydroxyl number 23.7

Acid value of 1.4

Molecular Weight (MW) ═ 4470 (calculated from acid number and hydroxyl number)

The polymer is characterized in that:

color: light brown

Viscosity: non-stick

Transparency: slightly translucent and slightly cloudy

Flexibility: crisp

Solid state

Example 3F (pigment Dispersion reagent)

This example illustrates the production of a carboxyl functional bio-derived polyester resin.

Equipment (see figure 5)

A 2 liter round bottom glass reaction vessel with a 4 neck top, jacketed wiggler column, distillation head, inlet and outlet gas adapters, stainless steel stirring shaft and 4-bladed (45 ° angle) paddle, condenser and receiving flask.

Flow path

The reactor was charged with D-isosorbide (545.35g, 3.7317 moles) (calculated as received), PripolDimer acid (batch No. 091687) (272.17g, 0.47302 moles) and 1, 4-cyclohexanedicarboxylic acid (1, 4-CHDA) (632.49g, 3.6734 moles), followed by antimony (III) oxide (0.498 g). The reactor was blanketed with argon. Then, 1, 2, 3, 4-tetrahydronaphthalene (2ml) was added to the reaction mixture under argon. The temperature of the reactor contents was raised to 200 ℃ under argon with stirring (after melting of the solid). This temperature was maintained for 30 minutes. The reaction mixture was slowly heated to 250 ℃ (1.6 ℃/min) over a period of 30 minutes. This temperature was maintained for 2.1 hours. Water was collected continuously as the reaction was heated above about 180 ℃. When the temperature at the top of the column drops, it indicates that most of the water has been removed. Approximately 134ml of water was distilled off. The flow rate of argon over the reaction was checked and reduced to a slow flow rate if necessary to avoid distilling off isosorbide. The reaction mixture was slowly heated to 280 deg.C (0.25 deg.C/min) over a 2 hour period. The distillate receiver was replaced with a vacuum receiver and vacuum (< 1 torr) was applied gradually. At this point, the residual water is distilled off and a low molecular weight polymer is formed. The reaction mixture temperature was maintained at 280 ℃ for 30 minutes. The reaction was terminated by blanketing the reaction mixture with argon to obtain atmospheric pressure. The reaction mixture was then cooled to 50 ℃ or less and poured onto a fluorinated fiber glass plate.

A resin was produced having the following properties:

T_g＝52.9℃

acid value of 47.7

Viscosity at 120 ═ 7772 poise

Viscosity at 160 ═ 247 poise

The polymer is characterized in that:

color: yellow/light amber color

Viscosity: non-stick

Transparency: semi-transparent

Flexibility: crisp

Solid state

The following example formulations 1 through 6 illustrate several exemplary toner formulations according to the present invention.

Formulation 1

Toner formulations were prepared using the polyester resin derived from isosorbide (corn derivative) and dimer diol (soybean derivative) of example 1 and carbon black from Cabot corporation.

It has been found that biogenic polyester toners are more difficult to micronize than standard original equipment manufacturer toners. This is mainly due to the higher molecular weight of the polyesters of biological origin. Typically, the toner has an average particle size of less than 30 microns. The average particle size of the biogenic polyester toner (resin plus colorant) was 24 μm. However, in another micronization test, the bio-derived polyester resin without carbon black was reduced to 14 microns in particle size. This means that the resin itself is processable.

TABLE 1 biogenic polyester toner resins comprising dimer diol

Developer formulation

Biogenic polyester toner 1.143g

17.862g of carrier FC-2 (Quartz Sand coated with methyl terpolymer)

Degussa R-972 (charge control agent) 0.011g

The average triboelectric charge was found to be-11.2 microcoulombs/gram. The blend of colorant was 90 wt% resin and 10 wt% carbon black.

Formulation 2

A toner formulation was prepared using the resin from example 3C. 90g of the soy-based resin from example 3C was blended with 10g of Raven 5250 CB on a Thropp 2 roller steam mill at a treatment temperature of about 285 ℃ F. and 300 ℃ F. for 20 to 30 minutes. Approximately 98.98 g of the blended material was recovered from the 2 roll mill.

The blended material was then crushed and mixed with dry ice until cold. The material was passed through hammer mill 1 and through a 10 mil screen and collected for micronization. The material recovered from the hammermill 1 was 50.56g (note: some material was spilled upon recovery). The hammer mill processed toner formulation was then micronized to the appropriate particle size (< 20 microns, volume average) using a Sturtevant air mill (air Sturtevant mill, model Mikropul #630) at a mill pressure of 87 psi, a feed pressure of 70 psi, and a No. 3 setting on a vibratory feed tray. The approximate material feed rate was 0.14 grams/minute.

The average particle size of the toner formulation was 11.7 microns in volume average diameter and 3.4 microns in number.

The developer was prepared with FC-2 carrier with 4% micronized resin and carbon black in the carrier. Toner formulation 2 gave an average triboelectric charge of about 14.2 microcoulombs/gram when mixed with the carrier. The resin is expected to have a sufficiently large negative charge to produce a good image.

Images were made with a type D scholar copier using the soy-based toner prepared from the resin or example 3C.

Preparation of formulation 3

90 grams of the carboxy functional soy resin from example 2 was blended with 10 grams of Raven 5250 CB. The same processing conditions and procedures were followed in the preparation of formulation 2. A negatively charged toner similar to formulation 2 was expected.

Preparation of formulation 4

This embodiment exemplifies a toner with negative frictional charge. 90 grams of the carboxy functional soy resin from example 3 was blended with 10 grams of Raven 5250 CB. The same processing conditions and procedures were followed in the preparation of formulation 2. Is expected to obtain

Formulation 2a similar negatively charged toner.

Preparation of formulation 5

This example illustrates the preparation of a toner having a positive triboelectric charge.

A toner prepared by milling 90 wt% of the resin from example 1 with 10 wt% of carbon black (from Cabot corporation) was blended in a Thropp 2 roll mill under the same conditions as for formulation 2. The toner was milled in a Sturtevant mill under the following conditions: a feed pressure of 60psi, a grinding pressure of 90psi and a feed rate of 0.2 grams/minute.

FBF-300 vector (Powdertech, Inc.) was used. The carrier has a core material of copper oxide (-14%), zinc oxide (-15%), and iron oxide (-71%), and is coated with silicone resin. The carrier was blended with the toner on a roll mill. The amount and type of carrier can be adjusted to control and achieve the desired triboelectric charge.

A toner having an average positive triboelectric charge of about +3.6 microcoulombs/gram was obtained. Although the amount of charge carried is less than desired, the lifting can be done using charge control agents.

Developer formulation 1

This example illustrates the preparation and use of developers, such as those associated with copiers that use negatively charged carriers and toners.

The toner used in this example was prepared according to formulation 2. The materials used for the developer were 200.0 grams of FC-2 carrier, 8.0 grams of micronized toner formulation, and 0.0418 grams of Aeorosil R-972 charge control agent. The average triboelectric charge obtained was-13.9 microcoulombs/gram.

The developer is used to produce images using a D-type Scherrer copier. The image transfer is good and has better image quality than that produced without the charge control agent.

Dispersion test

The resin of example 3F was evaluated for its pigment dispersibility with a color concentrate.

Materials:

two color masterbatch formulas are selected. One is a 10% Phthalocyanine Blue (PB)15:3(PB) loaded on a polystyrene carrier resin, and the other is custom green (custom green) in an acrylonitrile-butadiene-styrene copolymer (ABS) based carrier resin. The custom green consisted of a blend of organic and inorganic pigments and was loaded at approximately 18%. The control samples were tested with typical dispersants such as zinc stearate and a combination of zinc stearate and ethylene bis stearamide dispersant. And the samples were tested with the dispersant of example 3F.

Compounding:

compounding was carried out in a co-rotating 18 mm diameter Leistritz twin screw extruder.

And (3) testing:

the dispersion test was performed with the filtration test and the pressure build-up was reported with bar/gram of pigment. This is a quantitative test for dispersibility and lower values indicate better dispersibility.

Table 17 shows the formulations and results used for the tests.

TABLE 17

PB phthalocyanine Blue (Phtalo Blue)

ABS (acrylonitrile-butadiene-styrene) copolymer

EBS-ethylene bis stearamide

The mixture of EBS and zinc stearate showed good results compared to the dispersant zinc stearate on the market. The results show a consistently better color development in two different polymer systems.

The proteins disclosed in WO 04/077,169 are useful in the present invention. Such proteins useful in the present invention may be obtained from animal or vegetable sources, such as soy protein, corn protein, collagen, casein, endosperm (proteinalbumen), fish protein, and the like. Protein content in the toner can vary from about 0% to about 20% by weight is useful. More preferably from about 0.1% to about 10% by weight protein content. The protein provides improved deinking properties.

While the forms of the invention herein disclosed comprise preferred embodiments, many additional embodiments are possible. It is not intended herein to mention all of the possible equivalent forms or ramifications of the invention. It is to be understood that the terminology used herein is for the purpose of description and not of limitation, and that various changes may be made without departing from the spirit and scope of the invention.

Claims (15)

1. A thermoplastic toner composition comprising:

a mixture of the following materials in a mixture,

a. an amorphous thermoplastic polymer, which is capable of forming,

the amorphous thermoplastic polymer consists of a carboxyl-or hydroxyl-functional polyester, wherein the carboxyl-or hydroxyl-functional polyester is derived from a dianhydrohexitol, a first diacid moiety, and a second diacid moiety, optionally further comprising a monoacid; and the number of the first and second electrodes,

the first diacid is 1, 4-cyclohexanedicarboxylic acid and the second diacid is a dimer acid with 8 or more carbon atoms in the chain;

wherein the polymer is derived from at least one monomer of biological origin;

and the polymer has a T between 50 ℃ and 80 ℃_g；

b. A colorant dispersed in the amorphous thermoplastic polymer; and is

Wherein the toner composition is a powder having an average particle size of less than 30 microns.

2. The thermoplastic toner composition of claim 1 comprising the carboxyl-functional polyester having improved color dispersion properties.

3. The thermoplastic toner composition of claim 1, further comprising:

c. a protein.

4. The toner composition of claim 1, wherein the dianhydrohexitol includes an isosorbide moiety.

5. The toner composition of claim 1 wherein the carboxyl-or hydroxyl-functional polyester has a net biogenic content of at least 5 percent by weight.

6. The toner composition of claim 5, wherein the toner composition is a particle having an average particle size of less than 20 microns.

7. The toner composition according to claim 1, further comprising:

d. an excipient selected from the group consisting of charge control agents, flow control agents, lubricants, anti-caking agents, and mixtures thereof.

8. The toner composition of claim 1, wherein the toner composition has a negative or positive triboelectric charge of between 10 and 40 microcoulombs/gram.

9. The toner composition of claim 8 wherein said toner composition has a negative triboelectric charge of between 10 and 20 microcoulombs/gram.

10. The toner composition of claim 1, wherein the toner composition has a negative triboelectric charge.

11. The toner composition of claim 1 wherein the thermoplastic polymer comprises a polystyrene acrylate mixed with a polyester.

12. An image comprising

A substrate and a toner composition according to claim 1 applied on said substrate.

13. A toner, comprising:

(1) a thermoplastic polyester resin comprising:

A. a dianhydrohexitol;

B. an aliphatic dimer diol and/or dimer diacid, wherein the aliphatic dimer diol and/or dimer diacid comprises a six-membered ring having two side chains which are aliphatic side chains of 4 to 20 carbon atoms and two further side chains of 8 to 12 carbon atoms with an alcohol or carboxyl functionality;

C. a diacid, diester or diacid chloride, wherein,

the diacid, diester or diacid chloride has the general formula R₂-CO-R₁-CO-R₂，

Wherein R is₂is-OH, -OR₃or-Cl, wherein R₃Is an aliphatic chain having 1 to 4 carbon atoms, and R₁Is an aromatic or aliphatic group having 2 to 12 carbon atoms; and

D. optional catalyst

The reaction product of (a); and

(2) a pigment.

14. A developer, comprising:

(1) a thermoplastic polyester resin comprising:

A. a dianhydrohexitol;

B. an aliphatic dimer diol and/or dimer diacid, wherein the aliphatic dimer diol and/or dimer diacid comprises a six-membered ring having two side chains which are aliphatic side chains of 4 to 20 carbon atoms and two further side chains of 8 to 12 carbon atoms with an alcohol or carboxyl functionality;

C. a diacid, diester or diacid chloride, wherein,

the diacid, diester or diacid chloride has the general formula R₂-CO-R₁-CO-R₂，

Wherein R is₂is-OH, -OR₃or-Cl, wherein R₃Is an aliphatic chain having 1 to 4 carbon atoms, and R₁Is an aromatic or aliphatic group having 2 to 12 carbon atoms; and

D. optional catalyst

The reaction product of (a);

(2) a pigment; and

(3) and (3) a carrier.

15. The developer according to claim 14, wherein the developer further comprises a magnetic material.